JPH06258740A - Silver halide photographic emulsion and silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide photographic emulsion and the silver halide photographic sensitive material each high in sensitivity and improved in pressure desensitization and pressure fog and storage stability and low in fog. CONSTITUTION:The silver halide photographic sensitive material has at least one silver halide emulsion layer on a support, and it is characterized by containing, a silver halide grain in the dispersion medium of the silver halide emulsion in at least one layer of the photosensitive material, the silver halide grains >=50 numerical % of which contain total potassium ions in an amount of <=0.5weight% of the total silver weight in the emulsion and has >=10 dislocation lines in average per one grain.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material. More specifically, it relates to a silver halide color photographic light-sensitive material having high sensitivity, improved pressure desensitization and pressure fog, improved low fog and improved sensitivity decrease and fog increase after raw storage, and a silver halide photographic emulsion. .

[0002]

BACKGROUND OF THE INVENTION In recent years, with the increase in sensitivity of silver halide color photographic light-sensitive materials, there has been a strong demand for color photographic light-sensitive materials having higher sensitivity and excellent performances such as storage stability.

In connection with the trend toward higher sensitivity and higher image quality, the demand for improvement of pressure resistance in silver halide photographic light-sensitive materials has been increasing more than ever before.

Various pressures are generally applied to a photographic light-sensitive material coated with a silver halide emulsion. For example, a negative film for general photography is bent or rubbed when it is wound in a cartridge or loaded in a camera, and is also subjected to great pressure during cutting and processing.

As described above, it is generally known that various pressures are applied to the photographic light-sensitive material, and the photographic performance is changed, and a photographic material that does not change the photographic performance in response to these pressures is provided. There is a strong desire to do so.

As a means for improving the pressure characteristics, a method of incorporating a plasticizer such as a polymer or an emulsion or a method of reducing the silver halide / gelatin ratio of a silver halide emulsion is used to reach the pressure. It is known to prevent it. However, at present, it is difficult to achieve a sufficient effect by any of the methods.

In response to the demand for improved pressure characteristics, emulsions comprising core / shell type silver halide grains having a silver iodobromide layer having a high silver iodide content have been actively studied.

As an example of high sensitivity and improvement of pressure resistance,
An emulsion having a high silver iodide content inside a grain is disclosed in
59-99433, JP-A-60-35726 and JP-A-60-147726. However, when these examples were additionally tested, the effect of improving pressure resistance was insufficient.

Further, there is an example in which the silver halide grain structure is not a clear core / shell, but the iodine content in the grain is continuously changed to achieve high sensitivity and low pressure fog.
It is disclosed in Japanese Patent No. 3 publication. As a result, the effect of improving the pressure fog was obtained, but the pressure desensitization was significantly deteriorated.

Further, examples of achieving high sensitivity and low fog by forming silver halide grains in the presence of an oxidizing agent for silver include JP-A-3-89641, JP-A-3-194540 and JP-A-394540. -196135 etc. This is a technique for reducing fog by oxidizing the silver nuclei inside or on the surface of silver halide grains and has nothing to do with preservability or pressure resistance, particularly pressure desensitization.

Further, in JP-A Nos. 2-836 and 3-12645, gamma rays called environmental radiation generated by aging for a long period of time by reducing the potassium ion content in the light-sensitive material, A technique is disclosed in which the increase in fog caused by cosmic rays is reduced, the sensitivity is high, and the deterioration of graininess is suppressed as much as possible. However, in these conventional techniques, sufficient improvement effects have not been obtained with respect to pressure resistance, particularly pressure desensitization.

Further, JP-A-63-220238 and JP-A-1
-201649 discloses a technique in which dislocations are intentionally controlled and introduced into a tabular silver halide grain to improve sensitivity, graininess, pressure resistance and exposure illuminance dependency. However, in these conventional techniques, the introduction of dislocations is not completely controlled, and the storage stability is rather deteriorated, and various performances of silver halide emulsions have not been satisfactory yet.

[0013]

SUMMARY OF THE INVENTION An object of the present invention is to improve the above-mentioned problems and to provide a halogenated product having high sensitivity, improved pressure desensitization and pressure fog, low fog and further improved storage stability. The object is to provide a silver photographic emulsion and a silver halide photographic light-sensitive material.

[0014]

The above object of the present invention can be achieved by the following constitutions.

1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one layer in the light-sensitive material contains silver halide grains in a dispersion medium. In the silver emulsion, the total amount of potassium ions contained in the silver halide emulsion is 5 × 10 ⁻³ or less by weight ratio to the total amount of silver contained in the silver halide emulsion, and the average per grain is Halogenated grains having 10 or more dislocation lines contain a silver halide photographic emulsion which is 50% (number) or more of the silver halide grains contained in the silver halide emulsion. Silver photographic light-sensitive material.

2. It contains a silver halide emulsion in which dislocation lines are concentrated in a region of 0.5 L to L from the center of the grain with respect to the distance L from the center of the silver halide grain to the outer surface. 2. The silver halide photographic light-sensitive material as described in 1 above, wherein

3. The silver halide photographic light-sensitive material as described in 2 above, which contains a silver halide emulsion grain-formed in the presence of an oxidizing agent capable of oxidizing silver atoms.

4. A silver halide color photographic light-sensitive material characterized in that the oxidizing agent described in 3 above is a halogen element.

5. The silver iodide content in the grain of the emulsion is 10
.About.40 mol% of silver iodobromide phase is present, and this silver iodide phase is coated with silver halide containing lower silver iodide, and the surface of the grain is 6 mol% or less by XPS. 5. The silver halide photographic light-sensitive material as described in 4 above, which contains a silver halide emulsion containing

The present invention will be described in detail below.

In the present invention, the distance L from the center to the outer surface is defined as the distance between the center of the circle and the point intersecting the outer circumference of the particle when a straight line is drawn from the center of the circle to the outside.

In the present invention, the silver iodide content and the average silver iodide content of individual silver halide grains are determined by the EPMA method (Electro
This method, which can be obtained by using the n Probe Micro Analyzer method), produces a sample in which emulsion grains are well dispersed so that they do not come into contact with each other. Elemental analysis of small parts can be performed.

By this method, the halogen composition of each grain can be determined by obtaining the characteristic X-ray intensity of silver and iodide emitted from each grain. If the silver iodide content of at least 50 grains is determined by the EPMA method, the average silver iodide content can be determined from the average thereof.

In X-ray photoelectron spectroscopy, the emulsion is pretreated as follows prior to its measurement. First, about 1 ml of emulsion
Then, 10 ml of 0.01 wt% pronase aqueous solution is added, and gelatin is decomposed by stirring at 40 ° C. for 1 hour. Next, the emulsion particles are settled by centrifugation to remove the supernatant, 10 ml of an aqueous solution of pronase is added, and gelatin is decomposed again under the above conditions. After centrifuging this sample again and removing the supernatant, 10 ml of distilled water is added to redisperse the emulsion particles in distilled water, and the mixture is centrifuged to remove the supernatant. After repeating this washing operation three times, the emulsion grains are redispersed in ethanol (the work up to this point is performed in a dark room). This is thinly coated on a mirror-polished silicon wafer in a dimly lit room to obtain a measurement sample. The sample coated on the silicon wafer is measured by X-ray photoelectron spectroscopy within 24 hours.

For measurement by X-ray photoelectron spectroscopy, an ESCA / SAM560 type manufactured by PHI is used as an apparatus. The sample is fixed to a 60-degree tilt holder, evacuated for 10 minutes using a turbo molecular pump in the sample pre-evacuation chamber, and then introduced into the measurement chamber. Within 1 minute after sample introduction, excitation X-ray (Mg-Kα
(Line) is started and measurement is started immediately.

The X-ray source voltage is 15 kV and the X-ray source current is 40 mA.
Conduct under the condition of pass energy 50eV.

Ag 3d to determine the surface halide composition,
Br 3d and I 3d 3/2 electrons are detected. For the detection of Ag 3d electrons, the binding energy range from 381 eV to 361 eV is scanned step 0.2 eV, each step is measured once for 100 msec, and for the detection of Br 3d electrons, the total energy is scanned from 79 eV to 59 eV. Step 100msec is measured 5 times, and total energy of 644eV is 62 for detection of I 3d3 / 2 electrons.
Scans a range of 4 eV Step 0.2 eV, each step 100 mse
Measure 40 times for each c. The data is obtained by repeating the above operation twice.

The integrated intensity of each peak is used to calculate the composition ratio. The integrated intensity of the Ag 3d peak is 4 for the intensity of the energy value obtained by adding 4 eV to the total energy at which the Ag 3d 3/2 peak shows the maximum value and 4 for the binding energy at which the Ag 3d 5/2 peak shows the maximum value.
The straight line connecting the intensities of the added eV values was used as the baseline, and the integrated intensity of the Br 3d peak was 4 eV for the total energy at which the Br 3d 5/2 peak had the maximum value.
The base line is the straight line connecting the intensity of the added energy value and the intensity of the energy value obtained by subtracting 3eV from the total energy at which the Br 3d5 / 2 peak shows the maximum value, and the unit of cps ・ eV is used to calculate the integral of the I 3d3 / 2 peak. The intensity is a baseline that is a straight line connecting the intensity of the energy value obtained by adding 4eV to the total energy at which the I 3d3 / 2 peak shows the maximum value and the intensity of the energy value obtained by subtracting 4eV from the total energy at which the I 3d3 / 2 peak shows the maximum value. And cps · eV is used as the unit.

When the composition ratio is calculated from the integrated intensity of each peak, the relative sensitivity coefficient method is used and Ag 3d, Br 3d, I
By using 5.10, 0.81, and 4.592 as the relative powers of 3d3 / 2, respectively, the composition ratio is given in atomic percent. I mole percent is determined by dividing the atomic percent value of I by the atomic percent value of Br and the atomic percent value of I.

The emulsion of the present invention preferably has a more uniform iodine content between grains. The silver halide grains according to the present invention preferably have a more uniform iodide content between grains. When the distribution of iodide content between grains was measured by the EPMA method, the relative standard deviation was 35% or less.
It is preferably 20% or less.

The preferred halogen composition of the silver halide grain of the present invention is as follows. The average silver iodide content of the core portion is preferably 10 to 40 mol%, more preferably 15 to 40 mol%, and further preferably 20 to 40 mol%. The average iodine content of the shell portion is preferably 10 mol% or less, more preferably 5 mol% or less. The distribution of silver iodide in the shell part may be uniform or nonuniform.

The silver iodide content of the surface layer of the silver halide emulsion can be measured by XPS (X-ray photoelectron spectroscopy).

In the silver halide grain according to the present invention, if the silver iodide content of the surface layer of the silver halide emulsion is high, the chemically sensitized nuclei are dispersed, so that the storage stability is adversely affected. Therefore, in the silver halide grains according to the present invention, the silver iodide content of the surface layer of the silver halide emulsion is preferably 6 mol% or less, more preferably 4 mol% or less, and further preferably 2 mol% or less. .

Here, the surface layer of silver halide refers to a portion having a depth of about 50Å analyzed by X-ray photoelectron spectroscopy (XPS).

The silver halide grains according to the present invention are preferably composed of silver iodobromide having an average silver iodide content of 1 to 20 mol%, particularly preferably 3 to 15 mol%. Further, silver chloride can be contained within a range that does not impair the effects of the present invention.

The silver halide emulsion according to the present invention is characterized by the reduction of potassium ion contained in the emulsion.

The potassium ions are KCl and KB used for forming silver halide emulsion grains and adjusting the pAg of the emulsion.
It is introduced into the emulsion as r, KI or as an impurity in gelatin. Therefore, in order to reduce the amount of potassium ions contained in the emulsion in a large amount, it is necessary to consider changing the materials containing these potassium ions.

In addition to those contained in these emulsions, potassium ions are introduced into the silver halide light-sensitive material as a part of dyes and various additive chemicals. It is considered that the amount of potassium ion is small and the influence on the amount of potassium ion is small. The total amount of potassium ions contained in the silver halide emulsion according to the present invention is preferably 5 × 10 −3 or less, more preferably 1 ×, in terms of weight ratio to the total amount of silver contained in the silver halide emulsion. It is 10-3 or less, more preferably 5 × 10-4 or less.

Although several methods are known for analyzing the amount of potassium ions contained in the emulsion, for example, the analysis by the atomic absorption method is convenient.

There are also several known methods for analyzing the amount of silver contained in the emulsion. For example, atomic absorption method or elemental analysis using fluorescent X-ray is simple and easy. is there.

KI used for introducing dislocations according to the present invention and
The amount of NaI is preferably 0.01 to 5 mol%, more preferably 0.5 to 3 mol%, based on the host particles.

The dislocations of the silver halide grains relating to the present invention are described, for example, in JF Hamilton, Phot.Sci.Eng., Vol11,
57 (1967), T.Shiozawa, J.Soc.Phot.Sci.Japan, vol3
It can be observed by a direct method using a transmission electron microscope at low temperature described in 5, 213 (1972). In other words, the silver halide grains taken out carefully so as not to apply pressure enough to cause dislocation to the grains from the emulsion are placed on a mesh for electron microscope observation, and a sample is taken to prevent damage (printout etc.) due to electron beams. Observation is carried out by the transmission method in the state of being cooled. At this time, the thicker the particles, the more difficult it is for the electron beam to pass therethrough. Therefore, it is possible to more clearly observe using a high-voltage electron microscope (200 KV or more for particles having a thickness of 0.25 μm).

From the photograph of the grains obtained by such a method, the position and the number of dislocations of each grain when viewed from the direction perpendicular to the principal plane can be obtained.

The positions of dislocations in the silver halide grain according to the present invention are 0. from the center of the silver halide grain toward the outer surface.
It occurs in the area from 5L to L, but preferably 0.80
It occurs in the region of L to 0.98L. The direction of the dislocation line is approximately the direction from the center to the outer surface, but it often meanders.

Regarding the number of dislocations in the silver halide grains according to the present invention, 50% (the number) of grains containing 10 or more dislocations.
It is preferable that these exist. More preferably 80% (number) or more of particles containing 10 or more dislocations, and particularly preferably
It is preferable that 80% (number) or more of grains containing 20 or more dislocations are present.

The shape of the silver halide grains according to the present invention may be a regular crystal such as a cube, octahedron, or tetrahedron, or may be a twin crystal. When using tabular silver halide grains, the aspect ratio (average grain size / grain thickness ratio) is 1.3 to 20.
Is preferable, and particularly preferably 3 to 12.

The silver halide grains according to the present invention may be arbitrary such as a polydisperse emulsion having a wide grain size distribution and a monodisperse emulsion having a narrow grain size distribution. It may be a mixture of several emulsions. When a light-sensitive material is prepared using the silver halide grains of the present invention, it is preferably a monodisperse emulsion.

As the monodisperse silver halide emulsion, the weight of silver halide contained in the grain size range of ± 20% around the average grain size r is 60% or more of the total weight of silver halide grains. A certain amount is preferable, more preferably 70% or more, further preferably 80% or more.

Here, the average particle size r is defined as the particle size ri when the product ni × ri3 of the frequency ni of the particles having the particle size ri and ri3 becomes maximum (three significant figures and the least significant figure). Will be rounded to 4).

The term "particle size" as used herein means the diameter of spherical silver halide grains, and the diameter of a non-spherical grain whose projected image is converted into a circular image of the same area. Is.

The particle size can be obtained, for example, by magnifying the particles with an electron microscope from 10,000 times to 50,000 times and measuring the particle diameter on the print or the area at the time of projection (measurement). The number of particles shall be indiscriminately 1000 or more).

A particularly preferred highly monodisperse emulsion of the present invention is one having a standard distribution of (standard deviation) / (average grain size) × 100 = a distribution width [%] of 20% or less. Yes, and more preferably 15% or less.

The average particle size and standard deviation are obtained from the particle size ri defined above.

The silver halide grains according to the present invention may be those obtained by any of the acidic method, the neutral method and the ammonia method, and the method of reacting a soluble silver salt with a soluble silver halide is a side mixture. Any of a method, a simultaneous mixing method, and a combination thereof may be used.

It is also possible to use a method of forming grains in the presence of excess silver ions (so-called reverse mixing method). As one type of simultaneous mixing method, a method of keeping pAg constant in a liquid layer in which silver halide is produced, that is, a so-called controlled double jet method can be used.

Further, two or more kinds of silver halides formed separately may be mixed and used.

The silver halide grains according to the present invention are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), indium salt and rhodium during the grain forming process and / or the growing process. At least one selected from a salt (including a complex salt) and an iron salt (including a complex salt) can be used to add a metal ion to allow these metal elements to be contained inside and / or on the surface of the particle. A reduction sensitizing nucleus can be imparted to the inside of the grain and / or the surface of the grain by placing it in a different reducing atmosphere.

As a method for obtaining a monodisperse emulsion, two or more kinds of reactions arbitrarily selected from a water-soluble silver salt solution, a water-soluble halide solution, and silver halide fine particles in a gelatin solution containing seed particles. Elements can be obtained by adding under controlled pAg and pH. In determining the addition rate, reference can be made to JP-A-54-48521 and JP-A-58-49938.

As a method for obtaining a more advanced monodisperse emulsion, the growth method in the presence of tetrazaindene disclosed in JP-A-60-122935 can be applied.

A known silver halide solvent such as ammonia, thioether or thiourea may be present during the production of the silver halide grains according to the present invention, or the silver halide solvent may not be used.

The oxidizing agent of the present invention refers to a compound which acts on metallic silver to convert it into silver ions. In particular, a compound capable of converting extremely minute silver atoms generated in the process of forming silver halide grains into silver ions is effective.

The preferred oxidizing agent of the present invention is a halogen element, more preferably iodine.

The addition amount of the oxidizing agent to 1 mol of silver of the present invention is preferably selected from the range of 10 ^-7 to 10 ^-1 mol. It is preferably in the range of 10 ^-6 to 10 ^-2 mol, more preferably 10
^-5 to 10 ^-3 mol.

The oxidizing agent may be added to the reaction vessel before the grain growth, or may be added at any time from the grain growth to the chemical ripening. As a more preferable time, it is preferable to allow the particles to exist in the reaction vessel immediately before grain growth until desalting.

In order to add the oxidizing agent used in the present invention during the production process, a method usually used when adding an additive to a photographic emulsion can be applied. For example, photographic performance may be adversely affected by dissolving in water to form an aqueous solution having an appropriate concentration, or by using an appropriate organic solvent that can be mixed with water, such as alcohols, glycols, ketones, esters, and amides. You may melt | dissolve in the solvent which does not reach and may add as a solution. Alternatively, the solid may be added directly. The oxidizing agent may be added by rush addition, constant rate addition, or functional addition.

The silver halide grains according to the present invention are produced in the presence of a dispersion medium, that is, in a solution containing the dispersion medium.

Here, the aqueous solution containing a dispersion medium refers to an aqueous solution in which a protective colloid is formed by a substance that can form a hydrophilic colloid such as gelatin (a substance that can serve as a binder), and is preferably a colloid. An aqueous solution containing a protective gelatinous form.

When gelatin is used as the protective colloid in carrying out the present invention, the gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in Arthur Guice, The Macromolecular Chemistry of Gelatin, (Academic Press, 1964).

Hydrophilic colloids other than gelatin that can be used as protective colloids include, for example, gelatin derivatives, graft polymers of gelatin and other polymers,
Proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate, starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacryl Acid, polymethacrylic acid,
There are various types of synthetic hydrophilic polymeric substances such as polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, and other single or copolymers.

In the case of gelatin, it is preferable to use one having a jelly strength of 200 or more in the Paggy method.

The silver halide grain according to the present invention may be either a grain in which a latent image is mainly formed on the surface or a grain in which the latent image is mainly formed. The size of silver halide is 0.05 to 5.0. μm, preferably 0.1
~ 3.0 μm.

The silver halide grains according to the present invention may be those in which unnecessary soluble salts have been removed after the growth of the silver halide grains has been completed, or they may be contained as they are.

Further, as in the method described in JP-A-60-138538, it is possible to carry out desalting at any point of silver halide growth. The removal of the salts can be carried out according to the method described in Research Disclosure (hereinafter abbreviated as RD) No. 17643, Item II. More specifically, in order to remove the soluble salts from the emulsion after the formation of a precipitate or after the physical ripening, a Nudel water washing method performed by gelling gelatin may be used,
Alternatively, a precipitation method (flocculation) using an inorganic salt, an anionic surfactant, an anionic polymer (for example, polystyrene sulfonic acid), or a gelatin derivative (for example, acylated gelatin, carbamoylated gelatin, etc.) may be used.

The silver halide grains according to the present invention can be chemically sensitized by a conventional method. That is, a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, a noble metal sensitization method using a gold or other noble metal compound can be used alone or in combination. The silver halide grain according to the present invention can be optically sensitized to a desired wavelength range by using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more kinds. A dye that does not have a spectral sensitizing effect by itself with a sensitizing dye, or a compound that does not substantially absorb visible light, and that contains a supersensitizer that enhances the sensitizing effect of the sensitizing dye is included in the emulsion. May be.

Antifoggants, stabilizers and the like can be added to the silver halide grains according to the present invention. It is advantageous to use gelatin as the binder. The emulsion layer and other hydrophilic colloid layers may be hardened and may contain a plasticizer and a dispersion (latex) of a water-insoluble or soluble synthetic polymer.

A coupler is used in the emulsion layer of the color light-sensitive material. Further, by a coupling with a competing coupler having an effect of color correction and an oxidized product of a developing agent, a development accelerator, a developer, a silver halide solvent, a toning agent, a hardener, a fogging agent, an antifoggant, Compounds that release photographically useful fragments such as chemical sensitizers, spectral sensitizers and desensitizers can be used.

The light-sensitive material may be provided with auxiliary layers such as a filter layer, an antihalation layer and an anti-irradiation layer. In these layers and / or in the emulsion layers, dyes which may be bleached or bleached from the light-sensitive material during development processing may be contained.

Matting agents, lubricants, image stabilizers, formalin scavengers, ultraviolet absorbers, optical brighteners, surfactants, development accelerators and development retarders can be added to the light-sensitive material. As the support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate or the like can be used.

[0079]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 (Twinned Seed Emulsion T in which Halide Counterion is Sodium)
Preparation of -1) A seed emulsion T-1 having two parallel twin planes in which the halide counter ion was sodium was prepared by the following method.

(Solution A) Osein gelatin 80.0 g Sodium bromide 41.0 g Polyisopropylene-polyethyleneoxy-disuccinate sodium salt 10% methanol solution 0.48 ml Water is added to make up to 8000.0 ml.

(Solution B) Silver nitrate 1200.0 g 1600.0 ml with water (Solution C) Ocein gelatin 32.2 g Sodium bromide 683.1 g Sodium iodide 60.82 g Water is added to make 1600.0 ml.

(Solution D) Aqueous solution 470.0 ml Aqueous solution A was vigorously stirred at 40 ° C., and solution B and solution C were added by the double jet method in 7.7 minutes to generate nuclei.
During this time, pBr was kept at 1.60.

Thereafter, the temperature was lowered to 20 ° C. over 30 minutes. Further, the liquid D was added in 1 minute, and a 3.5N aqueous sodium bromide solution was additionally added, followed by aging for 5 minutes. The KBr concentration during aging was 0.10 mol / l and the ammonia concentration was 0.66 mol / l.

After completion of aging, the pH was adjusted to 6.0 and desalting was carried out according to a conventional method. When the seed emulsion grains were observed with an electron microscope, they were hexagonal tabular grains having an average grain size of 0.229 μm, a thickness of 0.13 μm and two twin planes parallel to each other (two parallel twin plane ratios). Is 72% of the total number of particles).

(Preparation of Silver Halide Emulsion in which Halide Counterion is Sodium and Introduction of Dislocation Line into the Emulsion) A tabular twin monodisperse emulsion for comparison was prepared using the following seven kinds of solutions. EM-1 was prepared.

(Solution E) Oscein gelatin 61.0 g Distilled water 1963.0 ml Polyisopropylene-polyethyleneoxy-disuccinate sodium salt 10% methanol solution 2.5 ml Seed emulsion (T-1) 0.345 mol 28% by weight aqueous ammonia solution 308.0 ml 56% by weight aqueous acetic acid solution 358.0 ml Make up to 20000.0 ml with distilled water.

(Solution F) 3.5N ammoniacal silver nitrate aqueous solution (however, pH was adjusted to 9.0 with ammonium nitrate) (Solution G) 3.5N sodium bromide aqueous solution (Solution H) 3% by weight of gelatin and silver iodide grains Fine particle emulsion composed of (average particle diameter of 0.05 μm) (*) 1.40 mol * The preparation method is shown below.

7.00 mol of silver nitrate and 7.06 mol of silver nitrate were added to 5000 ml of a 6.0% by weight gelatin solution containing 0.06 mol of sodium iodide.
2000 ml of an aqueous solution containing each mole of sodium iodide was added over 10 minutes. The pH during the formation of the fine particles is 2.
The temperature was controlled at 0 and the temperature at 40 ° C. After the particles were formed, the pH was adjusted to 6.0 with an aqueous sodium carbonate solution.

(Solution I) Fine grains composed of silver iodobromide grains (average grain size 0.04 μm) containing 2 mol% of silver iodide, prepared in the same manner as the silver iodide fine grain emulsion described in Solution H. Emulsion 3.68 mol However, the temperature during fine particle formation was controlled at 30 ° C.

(Solution J) 1.75N aqueous solution of sodium bromide (Solution K) 56% by weight aqueous solution of acetic acid Solution E was kept at 70 ° C. in a reaction vessel while vigorously stirring, and solution F, solution G and solution H were simultaneously added thereto. After 103 minutes by the mixing method, the solution I was added, and then the solution I was independently added at a constant rate over 7 minutes to grow a seed crystal.

Here, the addition rates of the solution F and the solution G were changed in a function-like manner with respect to time so as to be commensurate with the critical growth rate, and a large number of small particles other than the growing seed crystal were generated and Ostwald ripening was performed to increase the number. It was added at an appropriate addition rate so as not to disperse. The solution H, that is, the silver iodide fine grain emulsion is supplied by changing the rate ratio (molar ratio) with the aqueous ammoniacal silver nitrate solution with respect to the grain size (between additions) as shown in Table 1. Silver iodobromide emulsion EM having a composition
Created 1. Immediately before the addition of the aqueous ammoniacal silver nitrate solution, 33.7 ml of a methanol solution containing 450 mg of iodine (1 × 10 ⁻⁴ mol / mol silver) was added by rush.

By using the solutions J and K,
The pAg and pH during crystal growth were controlled as shown in Table 1. The pAg and pH were measured using a silver sulfide electrode and a glass electrode according to a conventional method.

After the grain formation, desalting treatment was carried out according to the method described in Japanese Patent Application No. 3-41314, and gelatin was added and redispersed to adjust pH to 5.80 and pAg to 8.06 at 40 ° C.
From the scanning electron micrograph of the obtained emulsion grains, the average grain size was 1.23 μm, the thickness was 0.23 μm (aspect ratio 5.3),
It was confirmed to be a tabular monodisperse emulsion having a distribution of 13.7%.

Further, crystals were grown from the seed emulsion T-1 by the same preparation method as for the emulsion EM-1, and when addition to the solution H was completed, an aqueous solution containing 26.5 g of sodium iodide 100 was added.
After adding ml at a constant rate over 1 minute and aging for 5 minutes,
Solution E was added in the same manner as Emulsion EM-1 to prepare Emulsion E of the present invention.
Created M-2.

Further, an emulsion EM-2 was prepared except that the rate ratio (molar ratio) of the solution H and the aqueous solution of ammoniacal silver nitrate during core formation was changed so that the amount of sodium iodide in the aqueous solution of sodium iodide was 2.65 g. Similarly, the emulsion EM-3 of the present invention was prepared.

Further, crystals were grown from the seed emulsion T-1 by the same preparation method as for the emulsion EM-1, and when the grain size reached 0.933 μm, addition of the solutions F, G and H was stopped and sodium iodide was added. 100 ml of an aqueous solution containing 2.65 g was slowly added over 1 minute, and after aging for 5 minutes, solutions F, G, and H were added again while changing the particle size (addition time), and then,
Solution E was added in the same manner as Emulsion EM-1 to prepare Emulsion EM of the present invention.
-4 was created. In this case, the silver iodide content in Solution I was 4 mol%.

[0098]

[Table 1]

(Preparation of Twin Crystal Seed Emulsion T-2 in which Halide Counterion is Potassium) A seed emulsion having two parallel twin planes in which the halide counterion is potassium is prepared by the following method. T-2 was prepared.

(Solution L) Ocein gelatin 80.0 g Potassium bromide 47.4 g Polyisopropylene-polyethyleneoxy-disuccinate sodium salt 10% methanol solution 0.48 ml Water is added to make up to 8000.0 ml. (Solution M) 3.5N ammoniacal silver nitrate aqueous solution (however, the pH was adjusted to 9.0 by ammonium nitrate) (Solution N) Ocein gelatin 32.2 g Potassium bromide 790.0 g Potassium iodide 70.34 g Water was added to make 1600.0 ml. (Solution O) Aqueous ammonia 470.0 ml The liquid M and the liquid N were added to the liquid L stirred vigorously at 40 ° C. for 7.7 minutes by the double jet method to generate nuclei.
During this time, pBr was kept at 1.60.

Thereafter, the temperature was lowered to 20 ° C. over 30 minutes. Further, liquid O was added in 1 minute, 3.5 N potassium bromide aqueous solution was additionally added, and aging was continued for 5 minutes. The KBr concentration during aging was 0.10 mol / l and the ammonia concentration was 0.66 mol / l.

After completion of aging, the pH was adjusted to 6.0 and desalting was carried out according to a conventional method. When the seed emulsion grains were observed with an electron microscope, they were hexagonal tabular grains having an average grain size of 0.238 μm, a thickness of 0.12 μm, and two parallel twin planes (two parallel twin plane ratios). Is 75% of the total number of particles).

(Preparation of silver halide emulsion in which halide counter ion is potassium and introduction of dislocation line into the emulsion) (Solution P) ossein gelatin 61.0 g distilled water 1963.0 ml polyisopropylene-polyethyleneoxy-di Succinate sodium salt 10% methanol solution 2.5 ml Seed emulsion (T-2) 0.345 mol 28 wt% ammonia solution 308.0 ml 56 wt% acetic acid solution 358.0 ml Distilled water to 20000.0 ml.

(Solution Q) 3.5N ammoniacal silver nitrate aqueous solution (however, the pH was adjusted to 9.0 with ammonium nitrate) (Solution R) 3.5N potassium bromide aqueous solution (Solution S) 3% by weight of gelatin and silver iodide grains Fine particle emulsion (*) composed of (average particle diameter of 0.05 μm) 1.40 mol * The preparation method is shown below.

(To 6.0 ml of a 6.0% by weight gelatin solution containing 0.06 mol of potassium iodide, 7.06 mol of silver nitrate and 7.06 mol of silver nitrate were added.
2000 ml of an aqueous solution containing each mole of potassium iodide was added over 10 minutes. The pH during the formation of fine particles was 2.0 using nitric acid.
The temperature was controlled at 40 ° C. After the particles were formed, the pH was adjusted to 6.0 with an aqueous sodium carbonate solution. (Solution T) A fine grain emulsion of silver iodobromide grains (average grain size 0.04 μm) containing 2 mol% of silver iodide prepared in the same manner as the silver iodide fine grain emulsion described in Solution S 3.68. However, the temperature during the formation of fine particles was controlled at 30 ° C.

(Solution U) 1.75N potassium bromide aqueous solution (Solution V) 56% by weight aqueous acetic acid solution Solution P was kept at 70 ° C. with vigorous stirring in a reaction vessel.
Solution Q, solution R and solution S are then added by the simultaneous mixing method.
After adding for 103 minutes, 100 ml of an aqueous solution containing 29.3 g of potassium iodide was added at a constant rate over 1 minute, and then 5
After aging for a minute, the solution T was continuously added independently at a constant rate over 7 minutes to grow a seed crystal. Here, the addition rates of the solution Q and the solution R are changed in a function-like manner with respect to time so as to be commensurate with the critical growth rate, and polydispersion does not occur due to generation of small particles other than the growing seed crystal and Ostwald ripening. Was added at an appropriate addition rate. The solution S, i.e., silver iodide fine grain emulsion, was supplied at a particle size (addition time) as shown in Table 2 with a velocity ratio (molar ratio) with the aqueous ammoniacal silver nitrate solution.
To produce a silver iodobromide emulsion EM-5 having a desired silver iodide composition. Immediately before starting the addition of the aqueous ammoniacal silver nitrate solution, 450 mg of iodine (1 x 1
0 ^-4 mol / mol Ag) in methanol 33.7ml containing added Rush. Further, by using the solutions U and V, pAg and pH during crystal growth were controlled as shown in Table 2. The pAg and pH were measured using a silver sulfide electrode and a glass electrode according to a conventional method.

After grain formation, desalting treatment was carried out according to the method described in Japanese Patent Application No. 3-41314, gelatin was then added and redispersed, and pH was adjusted to 5.80 and pAg was adjusted to 8.06 at 40 ° C.
From a scanning electron micrograph of the obtained emulsion grains, it was confirmed that the emulsion was a tabular monodisperse emulsion having an average grain size of 1.26 μm, a thickness of 0.22 μm (aspect ratio of 5.7) and a broad distribution of 13.6%.

Further, crystals were grown from the seed emulsion T-2 by the same preparation method as for EM-5, and when the grain size reached 0.933 μm, the addition of solutions Q, P and S was stopped and potassium iodide 2 was added. .
100 ml of an aqueous solution containing 93 g was added at a constant rate over 1 minute, followed by aging for 5 minutes, and then the solutions Q, R, and S were added again while changing the particle size (addition time), and then the emulsion 4 was added.
Similarly to the above, a solution T having a silver iodide content of 4 mol% was added to prepare a comparative emulsion EM-6. In this case, the iodine solution was not added.

Further, the solution P was kept at 70 ° C. in the reaction vessel while vigorously stirring, and the solution Q, the solution R and the solution S were added thereto.
The velocity ratio (molar ratio) with the ammoniacal silver nitrate aqueous solution
After adding for 103 minutes by the simultaneous mixing method while keeping at 8.0, solution T having a silver iodide content of 8 mol% was continuously added for 7 minutes at a constant rate for comparison. Emulsion EM-7 was prepared.

Also in this case, the iodine solution was not added.

Here, the addition rates of the solution Q and the solution R were changed in a function-like manner with respect to time so as to be commensurate with the critical growth rate, and a large number of particles other than the growing seed crystal were generated and Ostwald ripening was performed to increase the number. It was added at an appropriate addition rate so as not to disperse. The pAg and pH during crystal growth were controlled as shown in Table 2.

[0112]

[Table 2]

The dislocations of the emulsions EM-1 to EM-7 were directly observed with a transmission electron microscope. As an electron microscope, JEM-2000FX manufactured by JEOL Ltd. was used, and observation was performed at an acceleration voltage of 200 KV and a temperature of -120 ° C.

The content of potassium ions in the emulsion depends on the atomic absorption.
It was analyzed by a light method. The samples used for analysis are as follows:
It was adjusted by. 1 g of each emulsion H₂SO_Four5 ml and HN
O ₃After wet ashing with 3.5 ml, H₂Add O to make 10 ml
It was Also, only gelatin in the same amount as 1 g of emulsion is H₂SO_FourWhen
HNO₃Make 5 pieces with the same operation in.
Prepare a calibration curve solution by adding a known amount of potassium ion to
did. The measurement was carried out using an atomic absorption spectrophotometer made by Shimadzu Co., Ltd.
It was done in the mode. The same applies to silver ions.
After that, it was measured by an atomic absorption method.

The preparation conditions of the emulsions EM-1 to EM-7 and the obtained results are summarized in Table 3.

[0116]

[Table 3]

As can be seen from Table 3, generation of dislocation lines was found in the emulsion treated with potassium iodide during the growth of silver halide grains. The emulsion EM-2 of the present invention has a content of 0.
20 or more dislocation lines are generated in the 93L to 0.97L region. Emulsion EM-3 of the present invention has 10 or more dislocation lines in the region of 0.92L to 0.97L and EM-4 in the region of 0.62L to 0.96L. Also in the comparative emulsion, EM-5
EM-6 had a large potassium / silver ratio, but dislocation lines were found to occur as described above.

Example 2 (Preparation of Light-Sensitive Material Sample) Emulsions EM-1 to EM-7 were optimally subjected to gold-sulfur sensitization, and these emulsions were used to show the following on a triacetyl cellulose film support. Each layer having such a composition was sequentially formed from the support side to prepare a multilayer color photographic light-sensitive material.

In all the following descriptions, the addition amount in the silver halide photographic light-sensitive material is the number of grams per 1 m ² unless otherwise specified. Further, silver halide and colloidal silver are shown in terms of silver, and sensitizing dyes are shown in the number of moles per mole of silver halide.

The constitution of the multilayer color photographic light-sensitive material sample-1 (using the emulsion EM-1 of the present invention) is as follows.

First Layer: Antihalation Layer Black Colloidal Silver 0.16 Ultraviolet Absorber (UV-1) 0.30 Gelatin 1.70 Second Layer: Intermediate Layer (1L-1) Gelatin 0.80 Third Layer; Low Sensitivity Red Sensitive Layer (R- L) Silver iodobromide emulsion (average grain size 0.30 μm) 0.40 Sensitizing dye (S-1) 1.2 × 10 ⁻⁴ Sensitizing dye (S-2) 0.2 × 10 ⁻⁴ Sensitizing dye (S-3) 2.0 × 10 ^-4 Sensitizing dye (S-4) 1.2 × 10 ^-4 Cyan coupler (C-1) 0.33 Colored cyan coupler (CC-1) 0.05 High boiling point solvent (Oil-1) 0.30 Gelatin 0.55 Fourth layer; Medium Sensitive red-sensitive layer (RM) Silver iodobromide emulsion (average grain size 0.4 μm) 0.48 Sensitizing dye (S-1) 1.5 × 10 ^-4 Sensitizing dye (S-2) 0.2 × 10 ^-4 Sensitizing Dye (S-3) 2.5 × 10 ^-4 Sensitizing dye (S-4) 1.5 × 10 ^-4 Cyan coupler (C-1) 0.30 Colored cyan coupler (CC-1) 0.05 High boiling point solvent (Oil-1) 0.40 Gelatin 0.60 Fifth layer; high-sensitivity red-sensitive layer (RH) Silver iodobromide emulsion (average grain size 0.55 μm) 0.66 Sensitizing dye (S-1) 1.0 × 10 ⁻⁴ Sensitizing dye (S-2 ) 0.2 × 10 ^-4 sensitizing dye (S-3) 1.7 × 10 ^-4 sensitizing dye (S-4) 1.0 × 10 ^-4 Cyan coupler (C-2) 0.10 Colored cyan coupler (CC-1) 0.01 DIR Compound (D-1) 0.02 High boiling point solvent (Oil-1) 0.15 Gelatin 0.53 Sixth layer; Intermediate layer (1L-2) Gelatin 0.80 Seventh layer; Low sensitivity green sensitive layer (GL) Silver iodobromide emulsion (Average grain size 0.40 μm) 0.60 Silver iodobromide emulsion (Average grain size 0.30 μm) 0.40 Sensitizing dye (S-1) 0.6 × 10 ⁻⁴ Sensitizing dye (S-5) 5.1 × 10 ⁻⁴ Magenta coupler ( M-1) 0.55 Colored magenta coupler (CM-1) 0.17 DIR compound (D-2) 0.03 High boiling point solvent (Oil-2) 0.70 Gelatin 1.56 8th layer; High sensitivity green sensitive layer (G H) Silver iodobromide emulsion (emulsions of the invention EM-1) 0.60 Sensitizing dye (S-6) 1.5 × 10 -4 Sensitizing dye (S-7) 1.5 × 10 -4 Sensitizing dye (S-8) 1.5 × 10 ^-4 Magenta coupler (M-1) 0.06 Magenta coupler (M-2) 0.02 Colored magenta coupler (CM-2) 0.02 DIR compound (D-3) 0.002 High boiling point solvent (Oil-2) 0.15 Gelatin 0.45 9 layers; yellow filter layer (YC) yellow colloidal silver 0.12 HS-1 0.20 HS-2 0.14 high boiling point solvent (Oil-2) 0.18 gelatin 0.80 10th layer; low sensitivity blue sensitive layer (BL) silver iodobromide Emulsion (average particle size 0.4 μm) 0.18 Silver iodobromide emulsion (average particle size 0.3 μm) 0.35 Sensitizing dye (S-9) 5.1 × 10 ^-4 Sensitizing dye (S-10) 2.0 × 10 ^-4 Yellow coupler (Y-1) 0.58 Yellow coupler (Y-2) 0.30 High boiling point solvent (Oil-2) 0.15 Gelatin 1.20 11th Layer: High-sensitivity blue-sensitive layer (B-H) Silver iodobromide emulsion (average grain size 0.65 μm) 0.45 Sensitizing dye (S-9) 2.8 × 10 ⁻⁴ Sensitizing dye (S-10) 1.0 × 10 ^{− 4} Yellow coupler (Y-1) 0.10 High boiling point solvent (Oil-2) 0.04 Gelatin 0.50 12th layer; 1st protective layer (Pro-1) Silver iodobromide emulsion (average particle size 0.07 μm) 0.30 UV absorber ( UV-1) 0.07 Ultraviolet absorber (UV-2) 0.10 High boiling point solvent (Oil-2) 0.07 High boiling point solvent (Oil-3) 0.07 HS-1 0.25 Gelatin 0.80 13th layer; 2nd protective layer (Pro-2) ) Alkali-soluble matting agent (average particle size 2 μm) 0.13 Polymethylmethacrylate (average particle size 3 μm) 0.02 Gelatin 0.50 In addition to the above composition, coating aid Su-1, dispersion aid Su-2, hard film Agents H-1, H-2, Dyes AI-1, AI
-2 was added appropriately.

The structures of the compounds used in the above samples are shown below.

[0123]

[Chemical 1]

[0124]

[Chemical 2]

[0125]

[Chemical 3]

[0126]

[Chemical 4]

[0127]

[Chemical 5]

[0128]

[Chemical 6]

[0129]

[Chemical 7]

[0130]

[Chemical 8]

The emulsions EM-2 to EM-7 are also shown in Table 4.
As shown in, the emulsion EM-1 of Sample-1 was used in place of each of these emulsions to prepare multilayer color photographic light-sensitive material samples-2 to 7 in the same manner.

[0132]

[Table 4]

The processing steps are as follows.

Processing Steps 1. Color development 3 minutes 15 seconds 38.0 ± 0.1 ℃ 2. Bleach 6 minutes 30 seconds 38.0 ± 3.0 ℃ 3. Washing with water 3 minutes 15 seconds 24-41 ° C 4. Settling 6 minutes 30 seconds 38.0 ± 3.0 ° C 5. Washing with water 3 minutes 15 seconds 24-41 ° C 6. Stability 3 minutes 15 seconds 38.0 ± 3.0 ℃ 7. Dryness 50 ° C or less The composition of the treatment liquid used in each treatment step is as follows.

<Color developer> 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline / sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine / 1/2 sulfate 2.0 g anhydrous Potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Water is added to make 1 liter, and the pH is adjusted to 10.1.

<Bleach> Ethylenediaminetetraacetic acid ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water was added to make 1 liter, and pH was adjusted with aqueous ammonia.
Adjust to = 6.0.

<Fixer> Ammonium thiosulfate 175.0 g anhydrous sodium sulfite 8.5 g sodium metasulfite 2.3 g Water is added to make 1 liter, and pH is adjusted to 6.0 with acetic acid.

<Stabilizer> Formalin (37% aqueous solution) 1.5 ml Conidax (Konica Corporation) 7.5 ml Water is added to make 1 liter.

With respect to each of the obtained samples, relative sensitivity, fog and pressure fog, and pressure desensitization were evaluated using green light (G) immediately after preparation of the sample and after fresh storage. The raw storage conditions were 55 ° C. and 65% RH for 5 days.

The results are shown in Table 5.

[0141]

[Table 5]

The relative sensitivity is the relative value of the reciprocal of the exposure dose giving a density of Dmin (minimum density) +0.15, and is shown as a value with the sensitivity of Sample-1 as 100 (values for 100 are A larger value indicates higher sensitivity).

Relative fog is the relative value of the reciprocal of the exposure amount that gives the density of Dmin, and is shown as a value with the fog of Sample-1 as 100 (the higher the value, the higher the fog). Indicates). For pressure resistance, 23 ℃, 55%
Under a condition of (relative humidity), a scratch strength tester (manufactured by Shinto Kagaku Co., Ltd.) is used, and a needle having a tip radius of curvature of 0.025 mm is scanned at a constant speed with a load of 5 g, and then exposed and developed. The
For the pressure fog, the density change (ΔDpk) of the loaded part at the density of Dmin is obtained, and for the pressure desensitization, the density change (ΔDpg) of the loaded part at the density of Dmin + 0.4 is obtained. -1 ΔDpk
And ΔDpg are shown as a value of 100 (the smaller the value is, the better the improvement is).

As is clear from the results shown in Table 5, the samples-2, 3 and 4 of the present invention containing the emulsions EM-2, 3 and 4 according to the present invention have high sensitivity, improved fog and pressure. Fog and pressure desensitization are improved, and the preservability of these performances is also improved. Among them, Sample-2 using Emulsion EM-2 which satisfies the best combination of the present invention
Is especially good.

As described above, according to the invention of the present application, a silver halide photographic emulsion and a silver halide photographic light-sensitive material which are excellent in sensitivity, graininess and pressure desensitization can be obtained.

[0146]

INDUSTRIAL APPLICABILITY The silver halide photographic emulsion and the silver halide photographic light-sensitive material according to the present invention are excellent in pressure desensitization and pressure fog, and have low fog, and an image excellent in storability can be obtained.

Claims (5)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
In a silver halide emulsion containing silver halide grains in a dispersion medium in at least one layer of the light-sensitive material, the total amount of potassium ions contained in the silver halide emulsion is
Grains having a weight ratio of not more than 5 × 10 ⁻³ to the total amount of silver contained in the silver halide emulsion and having an average of 10 or more dislocation lines per grain are contained in the silver halide emulsion. A silver halide photographic light-sensitive material comprising a silver halide photographic emulsion which is 50% (number) or more of the silver halide grains. 2. A silver halide emulsion in which dislocation lines are concentrated in a region of 0.5 L to L from the center of the grain with respect to the distance L from the center of the silver halide grain to the outer surface. The silver halide photographic light-sensitive material according to claim 1, characterized in that 3. A silver halide photographic light-sensitive material according to claim 2, which contains a silver halide emulsion grain-formed in the presence of an oxidizing agent capable of oxidizing silver atoms. 4. A silver halide photographic light-sensitive material, wherein the oxidizing agent according to claim 3 is a halogen element. 5. The silver iodide content within the grain of the emulsion is 10 to 10.
40 mol% of silver iodobromide phase is present, and this silver iodide phase is coated with silver halide containing a lower silver iodide, and the surface of the grain contains 6 mol% or less of silver iodide by XPS. 5. The silver halide photographic light-sensitive material according to claim 4, which contains a silver halide emulsion containing it.